N-(alkylhalophenyl) derivatives of leucauramine



N-(ALKYLHALOPHENXL) DERIVATIVES OF LEUCAURAMINE Clyde S. Adams, YellowSprings, and Marjorie I. Cormack, Dayton, Ohio, assignors to TheNational Cash Register Company,.,-l )ayton, Ohio, a corporation ofMaryland No Drawing. Application January 10, 1956 Serial-No.-558,-194

. er i g. v c1. zoo- 579 invention relates to the c=N-(alkylhaloph enyl)derivatives-of leucaurarnine, having the; general; structure (CHa)zN trisilicate, and zinc sulphide, among others, and are useful in solutionfor printing in color on paper coated or filled with such adsorbents.Otherwise, they are very lightstable and atmospherically-stable bothqintheir leucauramine forms and in their colored states.

The great utility of these compounds, as at present known, is their usein transfer coatings in manifold record systems wherein the rear surfaceof an overlying sheet of record material is coated with a compositioncontaining one or more of the novel leucauramine derivatives and theunderlying sheet containing particles of the acidic reactant. In suchmanifold systems the leucauramine derivatives or mixtures of them, areusually dissolved in a-suitable solvent and carried as droplets in ahydrophilic colloid film coatingon the, rear oftheoverlying sheet. Whenthe two sheets are in contact and a printed or written impression ismade on the top surface of the overlying sheet, rupturing the film atthe points of pressure, the liquid solution is released locally so itmay be adsorbed by the acidic particles in or on the under sheet. Suchcontact will make blue or blue-green marks on the top surface of theunder sheet at the points of pressure. Such a manifold system isdisclosed in United States Patent 2,712,507 which issued July 5, 1955,on the application of Barrett K. Green.

These alkylhalo derivatives of N-phenyl leucauramine are much moresuitable for the manifold systems mentioned than the unsubstituted knownN-phenyl leucauramine, because they are less volatile, they haveincreased solubility in oil, and they are much more stable compounds inthe leuco form when subjected to the atmosphere and'light.

The leucauramine derivatives also. are useful .in, solid powdered formasone of two solid .powdered materials 5 placed by an alkylhalosubstituted phenyl group.

sheet, the second material being one of the acidic inorganic materialswhich cause a blue orblue-green color to appearwhen'marked with astylus. Such a record sheet is disclosed in' jUnited StatesPatent2,505,470 which issued, on the application ofia-Barrett K. Green, onApril 25, 1950.

One process of--making the novel compounds consists of the stepsofqicondensing molar equivalents of Michlers hydrolan'd aiselectedalkylhalo derivative of aniline in hot ethyhalcohol; concentrating thereaction mixture 'as far as necessary to cause precipitation on cooling;filtering;.puri fying the crude materialby heating a benzene solutionof'it .with fullerswearth and activated charcoal; and thenprecipitatingout the reaction product by'the addition of petroleumether. jThe general equaftion'for this reactionis as' follows:

. Michlers, ydrol alkylhalo substituted aniline (one-2N The novelderivatives of this invention may be con- 50 sidered as derivativesofleucauramine in that one of the hydrogen atoms attached tothe (1) N hasbeen replaced by an alkylhalo substituted phenyl group.

Asa first-specificexample of theprocess, consider the making of'N-(2-methyl;5-chlorophenyl )leucauramine;

0 in a round-bottomed flask fitted with a water-cooled reflux condenser.The solution is refluxed for four hours on a steam bath after which thesolution is allowed to cool to room temperature. The crystals which haveseparated out are filtered off by suction and washed with small amountsof cold ethyl alcohol. The filtrate may be concentrated for additionalcrops of crystals. The resultant crude product is dissolved in 1% litersof hot benzene, treated with activated charcoal, and fullers earth, andfiltered. The filtrate is evaporated to approximately 200 milliliters,cooled, and the reaction product precipitated out with petroleum ether.The resulting pure material is 3. a white crystalline substance.Following is a representation of the reaction:

+ non The other methylchloro and methylbromo derivatives mentioned inthe first paragraph of the specification may be made by using amethylchloro or methylbromo aniline with the methyl and chloro or bromosubstitue'nts'in the desired positions, in the same procedure justoutlined with respect to the preparation of N-(2-methyl,5-chlorophenyl)leucaurarnine, the molecular proportions being the same.

A typical N-(methylbromophenyl)leucauramine is prepared as follows:

93 grams (0.5 mole) of aniline with the bromo and methyl substituents inthe desired positions as selected from those set forth in the firstparagraph of the specification.

135 grams (0.5 mole) and of Michlers hydrol are dissolved in 200 gramsof ethyl alcohol and the before-mentioned procedure outlined for thepreparation of the methylbromo derivatives is followed. The reaction isrepresented as follows:

Miehlers Hydro] Methylbromo substituted aniline (CH3)2N N(CHs) HOE lIITH X N-methylbromophenyl leucauramlne It will be obvious to thoseskilled in the art that the ethylhalo or higher alkylhalo homologs ofN-(alkylhalophenyl) derivatives of leucauramine may be made in the samemanner by use of the selected substituted aniline in the same molecularamounts.

.4 What is claimed is: 1. The derivative compounds ofN-(alkylhalophenyD- leucauramine, having the general structure mN N(Hs)2 where RX is taken fromthe group consisting of Z-chloro, 3-methyl;2-bromo,3-methyl; 2-methyl,3- chlor0; Z-methyl, S-bromo;2-chloro,4-methyl; 2-bromo,4-methyl; Z-methyl, 4-chloro;2-methyl,4-bromo; 2-chloro,5-methyl; Z-bromo, S-methyl;2-methyl,5-chloro; 2-methyl,5-bromo; 3-chloro, 4-methyl;3-bromo,4-methyl; 3-methyl,4-chloro; 3-methyl, 4-bro1no;3-rnethyl,5-chloro; and 3-chloro,5-methyl.

2. The compound N-(Z-chloro,5-methlyphenyl)1eucauramine, having thestructure 3. The compound N-(Z-metyhLS-chlorophenyl)leucauramine havingthe structure (CHahN-e 4. The compound N(2-methyl,4-bromophenyl)leucaurarnine, having the structure a)zN 7References Cited in the file of this patent Ben, 35, 358-375 (1902).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No,2,828,342 March 25, 1958 Clyde 5. Adams et a1.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction and that the saidLetters Patent should readas corrected below.

Column 2, line 5-, strike out "placed by an allgylhalo substitutedphenyl group," and insert instead dispersed in a coating on one side ofa record material column 4, line 33, for "metyhl" read methyl Signed andsealed this 27th day or May 1958.

(SEAL) Attest:

KARL AXIINE ROBERT c. WATSON Attesting Officer Conmissioner of Patents

1. THE DERIVATIVE COMPOUNDS OF N-(ALKYLHALOPHENYL)LEUCAURAMINE, HAVINGTHE GENERAL STRUCTURE